LT7025B - Method of manufacturing an electrochemical cell and an electrochemical cell - Google Patents

Abstract

A method of manufacturing an electrochemical cell and an electrochemical cell so obtained is disclosed. The method comprises providing a multi-layered ceramic-metal capacitor, removing insulating coating at a side area of the capacitor to expose side edges of ceramic dielectric material and metallic plates of electrodes. The opening is covered with insulating material so that terminals of the electrodes could be coated with insulating material. The cover of the opening is removed and edges of plates of the electrodes are functionalised by electrochemical plating. The terminals of the electrodes are connected to signal transmitting means for transmitting signals from the electrodes. One or more pairs of such electrodes are obtained in such way to form a multi-electrode electrochemical system. Electrode system can be placed in any type of electrochemical cells including designing of multiple electrochemical cells within multi-wailed) plates of enzyme linked immune sorbent assay (ELISA)-plate or similar multi-wailed systems.

Description

TECHNICAL FIELD

The invention relates to miniaturized electrochemical systems suitable for any type of electrochemical cells (cells).

STATE OF THE ART

Electrochemical cells are used in various fields of activity. Their design varies depending on the type of electrochemical systems, needs and areas of application. Miniaturized electrochemical cells have been applied in sensors and biosensors for some time. However, both electrodes and electrochemical cells are currently manufactured using time-consuming manufacturing processes that are at least partially performed by humans or mechanized systems, for example, electrodes can be formed by melting metal rods or wires in glass; or insulating with electrically non-conductive ceramics or plastic; or the electrodes are formed by screen printing or photolithography methods. However, these methods are quite time-consuming and are not always easily compatible with the automated methods and hardware that are used in the latest microelectronics construction devices. Therefore, in the development of integrated electrochemical devices based on standard microelectronics, new principles of formation of electrodes and/or entire electrochemical cells (eg: electrochemical cells) are required. Another very important technological parameter of electrochemical systems is the reduction of the dimensions of the electrodes, which makes it possible to reduce the background noise of the sensor and at the same time to increase the sensitivity and/or selectivity of electrochemical sensors.

Conventional technologies and methods have recently been used for the development of electrochemical cells, which are characterized by the following disadvantages: fusing metal wires in glass or sealing them in electrically non-conductive ceramics or plastics is a rather long procedure, which usually requires quite a number of technological steps, which are sometimes performed by a person - "manually" way"; electrodes created by such methods have relatively large dimensions; although screen printing techniques can also be applied to the above purposes and can be automated, they are not easily integrated into electronic board assembly equipment, and screen printing techniques often require the use of harmful solvents and solutions and relatively high temperatures of over 120°C to form for drying structures; photolithography can also be applied for the above purposes, but it is a rather complex multi-step procedure that must be performed in the modification of the electrical board before the integration of other microelectronic components.

In US patent application no. US15/749,257 describes a multilayer ceramic/metal type gas sensor and a method of manufacturing the same. The body of the gas sensor is composed of a multilayer ceramic/metal structure with multiple parallel layered structures of ceramic dielectric material and metal. The sensor body consists of at least one such layered structure, in which the first inner electrode and the second inner electrode are sequentially layered, which are separated by a layer of ceramic dielectric material. The first inner electrode and the second inner electrode are partially exposed. The first internal electrode is electrically connected to the first electrode terminal on the first side of the sensor housing, and the second internal electrode is electrically connected to the second electrode terminal on the second side of the sensor housing facing the first side. The first and second internal electrodes are exposed to form a working surface on at least one side of the sensor body other than the side where the first and second electrode terminals are mounted. A gas-sensitive material layer for gas detection is formed on part or all of the upper surface of the sensor or a metal film whose contact resistance with the gas-sensitive material layer is lower than that of the first layer, and the second internal electrode is formed on the upper part of the first and second internal electrodes , which is exposed, and a layer of gas-sensitive material for gas detection is formed on part or all of the upper part of the sensor surface where the metal film is formed. This invention is intended exclusively for the production of gas sensors and is suitable for use only in analysis in gaseous environments.

The performance of electrochemical systems containing liquids and/or liquid electrolytes is very different from that of systems operating in a gaseous environment. Therefore, such electrochemical systems are much more complex, and for this reason, the development of electrochemical systems is much more complicated than the development of analytical systems for gas analysis, which are based on the simple measurement of the change in resistance between two electrodes.

The invention described in this application is intended to eliminate the above-mentioned disadvantages and to achieve additional advantages compared to the prior art, making it possible to apply any type of commercial multilayer metal-insulator capacitors in electrochemical systems (electrochemical cells).

ESSENCE OF THE INVENTION

The present invention is a method of forming a system of electrochemical cells (cells) comprising at least one modified multilayer ceramic/metal plate microcapacitor with connected electrodes. The conductive electrode plates of a multilayer ceramic/metal microcapacitor of this size are several hundred nanometers to several hundred micrometers thick, depending on the design. The thickness of the ceramic dielectric material between the mentioned electrode plates is also in the range of several hundred nanometers. Therefore, in the way described below, very thin electrode systems can be designed and interconnected and variously connected, which is very difficult to achieve with other currently widely used technological methods. The method includes providing a multilayer ceramic/metal capacitor, wherein said capacitor comprises a layered structure composed of a ceramic dielectric material (1), a first internal electrode (2) and a second internal electrode (3), wherein the layered structure is coated with a dielectric coating (4). and partially removing the dielectric coating (4). The method further includes partially removing the dielectric coating (4) and forming an open region (5) on one side of the multilayer ceramic/metal capacitor to expose the layered ceramic dielectric material (1), the first internal electrode (2) and the second internal electrode (3 ), where both internal electrodes are adapted to the structure of the electrochemical cell, sides (2'', 3''). The open area (5) can be formed during the production of the capacitor, leaving this part of the ceramic/metal capacitor uncovered with an insulating layer, the open area (5) can also be formed by exposing already after the formation of the electro-insulating coating, using abrasive materials and/or grinding, grinding and polishing devices and/or removing the removable protective tape attached at the beginning of the process. After that, conductive parts (8', 8'), such as wires, insulated wires (8') and/or electrically conductive tracks (8"), are used on the electrical component mounting plate to form electrical contacts between the electrodes (2, 3) and to transmit the signals generated by the electrodes, are connected to the connections (6, 7) of the electrodes (2, 3). Later, the open area (5) is covered with an easily removable layer of protective material (9), such as protective tape or other easily removable protective material, which protects the working area from being covered with an additional layer of dielectric material. Part of the multi-layer metal electrode terminals (6, 7) and part of the electrodes (2, 3) are coated with a waterproof dielectric material in order to protect the contacts (6, 7) from solutions and solvents used in the following operations of the first and second electrodes (2, 3) side (2'', 3'') modifications. After that, the easily removable layer of protective material (9) is removed from the exposed area (5) and the sides (2'', 3'') of the first and second electrodes (2, 3) are exposed again for further modification steps. After that, the multilayer capacitor is completely immersed in a solution for the electrochemical deposition of metal and/or other modifying substances on the exposed sides (2'') of the first electrode (2), where an electric potential is applied to the contact (6) of the first internal electrode (2). , connecting the plates of the first internal electrode (2). The first contact (6) is connected to the corresponding input of the potentiostat/galvanostat, while the contact (7) of the second internal electrode (3) is disconnected at the time. Later, the solution for the electrochemical deposition of metal and/or other modifying substances is changed and electrochemical deposition of metal and/or other modifying substances is performed on the open sides (3'') of the second electrode (3) by applying an appropriate electrical potential to the contact of the second electrode (3) ( 7), connecting the second contact (7) to the corresponding input of the potentiostat/galvanostat, while the contact (6) of the first electrode (2) is disconnected at that time. In the last step, the electrodes (2, 3) are at least partially immersed in a liquid electrolyte solution, forming an electrochemical cell.

In this way, it is also possible to form multi-channel electrochemical cells, which can be used by integrating them with enzyme-linked immunosorbent assay (ELISA) plates or similar multi-channel analytical systems.

In one multilayer ceramic/metal-based capacitor, two separate electrode plates are electrically connected to each other, resulting in an ideal multilayer structure of sunken electrodes after the described modification, suitable for the formation of various electrochemical systems that can be applied to various electrochemical devices, including batteries, rechargeable batteries, electrolytic capacitors, electrochemical sensors, electrochemical biosensors, electrochemical fuel and biofuel cells.

In electrochemical systems formed in this way, two or more electrodes can be formed, using any one or more capacitors.

BRIEF DESCRIPTION OF THE DRAWINGS

The features of the invention which are new and innovative are disclosed in detail in the appended claims. However, the invention itself may be best understood by reference to the following detailed description of the present invention, in which exemplary embodiments of the invention are set forth by way of non-limiting examples, together with the accompanying drawings, in which:

Fig. shows a commercially available multilayer ceramic/metal capacitor consisting of two electrodes.

Fig. shows the step of removing the outer insulating layer of a multilayer ceramic/metal capacitor to expose the sides of the ceramic dielectric material and the sides of the first electrode plates and the sides of the second electrode plates.

Fig. shows the step of attaching protective tape or other easily removable covering material over the exposed area and attaching a single multilayer capacitor to the mounting plate.

Fig. shows the step of attaching protective tape or other easily removable covering material over the exposed areas of two multilayer capacitors and mounting the two capacitors on a mounting plate.

Fig. shows covering the electrode contacts with protective tape or other easily removable protective material to protect the electrode contact parts of the multilayer capacitor and the surface of the mounting plate from being covered with an additional layer of insulating material during subsequent modification steps.

Fig. is shown covering the electrode contacts with protective tape or other easily removable protective material to protect the electrode contact parts of the two multilayer capacitors and the surface of the mounting plate from being covered with an additional layer of insulating material during subsequent modification steps.

Fig. shows the formation of a dielectric layer on the electrically conductive parts of the capacitor, which must be insulated to avoid direct contact with the solution.

Fig. shows the formation of a dielectric layer on the electrically conductive parts of two capacitors, which must be insulated to avoid direct contact with the solution.

Fig. shows the step of removing the insulating material from the exposed area of one capacitor.

Fig. shows the step of removing the insulating material from the exposed areas of the two capacitors.

Fig. shows the step of immersing a capacitor in a solution used for electrochemical deposition of metal and/or other modifying materials on the sides of one capacitor's electrode plates.

Fig. shows the step of immersing a capacitor in a solution used for electrochemical deposition of metal and/or other modifying substances on the edges of two capacitor electrode plates.

Fig. shows the step of immersing a capacitor in a solution used for electrochemical deposition of metal and/or other modifying materials on one side of the capacitor's electrode plates into a well of the ELISA system. The same figure shows the potential application of an electrochemical cell based on an ELISA system for analytical purposes.

Fig. shows the electrode arrangement of an electrochemical cell consisting of two multilayer ceramic/metal capacitors in a four-electrode system, where each capacitor consists of two electrodes: one electrode of each capacitor is the working electrode, of any of the two capacitors, one of the remaining electrodes is the reference electrode and the remaining electrode is the auxiliary electrode.

Fig. shows the arrangement of electrodes in an electrochemical cell consisting of two multilayer ceramic/metal capacitors in a three-electrode system, where each capacitor consists of two electrodes: the electrode of one capacitor is the working electrode, the other electrode of the same capacitor is the reference electrode, and both electrodes of the second capacitor are auxiliary electrodes.

Fig. shows an embodiment of an electrochemical cell using two electrodes of a single multilayer capacitor in a two-electrode system according to the invention.

Fig. the system of an electrochemical cell consisting of two multilayer capacitors with four electrodes is shown. Such a system is suitable for both three- and four-electrode electrochemical cell configurations.

Fig. is shown of several electrochemical cells on an enzyme-linked immunosorbent assay (ELISA) plate. The same figure shows the potential application of several electrochemical cells in ELISA plates with multilayer ceramic/metal capacitor electrodes for electroanalytical purposes.

Fig. the cyclic voltammogram of the electrochemical system, recorded during the realization of Fig. 17, is shown. depicted system in which the working electrode used is made of pure (unmodified) titanium Ti; the reference electrode is a silver coated electrode, an electrochemically formed silver/silver chloride Ag/AgCl electrode; the auxiliary electrode is paved with a set of interconnected unmodified titanium electrodes. The assay was performed in 0.1 M phosphate buffer solution with 0.01 KCl.

Fig. an example application of an electrochemical cell consisting of two capacitors operating in a three-electrode configuration as shown in Fig. 15 for an amperometric glucose biosensor is depicted.

Fig. amperometric responses to different glucose concentrations in the three-electrode mode of the glucose biosensor designed according to the scheme presented in Figure 20 are shown. The amperometric measurement was performed when the working electrode was set at a potential of +800 mV, relative to the reference Ag/AgCl electrode. Arrows indicate the concentration of glucose added to the solution.

Fig. are shown amperometrically measured responses of a glucose biosensor, measured in an electrochemical system constructed according to the scheme shown in Figure 20, in three-electrode mode, at different glucose concentrations.

Fig. amperometrically measured electrochemical systems constructed according to Fig. 16 are shown. the presented scheme, in the two-electrode mode, responses to different concentrations of hydrogen peroxide (H2O2).

Preferred embodiments of the invention are described below with reference to the accompanying drawings. Each figure uses the same numbering of the same or equivalent elements.

DETAILED DESCRIPTION OF METHODS FOR IMPLEMENTING THE INVENTION

The description contains many specific details in order to provide a complete and comprehensible description of the implementation of the invention. A description is provided for those skilled in the art, and it should be noted that the examples provided include applications of the invention that may be practiced without the specific instructions provided herein. To avoid redundant information, well-known methods, procedures, and components are not described in detail. Further, this description is not intended to limit the invention to the embodiments provided herein, but only as one of many possible embodiments of the invention.

The manufacturing method of the electrochemical cell according to the invention includes the use of a multilayer ceramic/metal capacitor (C) with a general structure, for example, a multilayer ceramic/metal microcapacitor (C) as shown in Figure 1, where the multilayer ceramic/metal microcapacitor (C) includes many sequentially arranged layers a structure as shown in Figure 2, consisting of repeated layers of ceramic dielectric material (1) and metal plates (2', 3') and an insulating coating (4) to encapsulate and isolate the layered structure of the capacitor (C) from other parts of the electrical circuit. The first set of metal plates (2') consists of the plates of the first internal electrode (2), and the second set of metal plates (3') consists of the plates of the second internal electrode (3), where the sequence of layers is such that between each metal plate (2 ', 3') a layer of ceramic dielectric material (1) is formed. Each first metal plate (2') is connected to form a first electrode (2), and each second metal plate (3') is connected to form a second electrode (3).

In all embodiments of the present invention, the electrodes are electrically conductive.

In all embodiments, the multilayer ceramic/metal microcapacitor includes electrodes of interlocking plates. Therefore, after the pretreatment described in the subsequent modification steps, an ideal structure of intercalated electrodes is formed, which is suitable for various electrochemical systems.

An open area (5) is formed on at least one side of the multilayer ceramic/metal capacitor (C) by removing part of the insulating coating (4) from the side of the layered structure and exposing the sides of the layers of the ceramic dielectric material (1), the metal plates of the first internal electrode (2) ( 2') sides (2'') and sides (3'') of the metal plates (3') of the second internal electrode (3).

The sides (2'', 3'') of the first and second electrodes (2, 3) are exposed to form a working area, e.g. sensory area. The exposed area (5) is formed during the manufacturing process or, if a ready-made ceramic/metal capacitor (C) is used, the exposed area of the capacitor is formed with abrasives and/or abrasives, a grinding or polishing device to remove the insulating coating (4) from the first and the surface of the sides (2'', 3'') of the second electrode (2, 3). After removing the electro-insulating coating (4), the sides (2'', 3'') of the first and second electrodes (2, 3), together with the sides of the layers of ceramic dielectric material (1) between them, are polished using fine abrasive materials such as as AbOa, and/or a grinding or polishing device.

As shown in Figure 3, the open area (5) of the capacitor is then covered with an easily removable layer of protective material (9), which protects the working surface area from being covered with a long-term insulating material. The easily removable layer of protective material (9) is formed to cover and protect the exposed sides (2'', 3'') of the first and second electrodes (2, 3) and the sides of the ceramic dielectric material (1) between these electrodes.

The method includes connecting the first internal electrode (2) to the electrode contact (6) located at one end of the capacitor (C) and connecting the second internal electrode (3) to the electrode contact (7) located at the second end of the capacitor (C) opposite the first end . The same applies if two or more capacitors are used instead of one, as shown in Figure 4.

As shown in Figure 5, the method additionally includes connecting the electrical signal transmission means (8', 8'') to the contacts (6, 7) of the electrodes (2, 3) for transmitting signals from the working area. Signal transmission means (8', 8) can be insulated wires (8') and/or electrically conductive tracks (8) formed in an electronics mounting plate for mounting a multilayer ceramic/metal capacitor and/or a matrix of such capacitors. The same principles apply if two or more capacitors are used instead of one, as shown in Figure 6.

As shown in Figure 7, later, the contacts (6, 7) of the electrodes (2, 3) are coated with a permanent insulating material (11) to protect the contacts (6, 7) from contact with the solutions of the following, first and second electrodes (2, 3) during modification of the sides (2'', 3''). The same principles apply if two or more multilayer ceramic/metal capacitors are used instead of one, as shown in Figure 8.

As shown in Figure 9, the previously formed easily removable protective material layer (9) is removed from the exposed area (5), exposing the sides (2'', 3'') of the first and second electrodes (2, 3) for further modification. The same principles apply if two or more capacitors are used instead of one, as shown in Figure 10.

After that, the multilayer capacitor (C) is completely immersed in a solution for the electrochemical deposition of metal and/or other modifying substances on the exposed sides (2'') of the first electrode (2). An electrical potential is applied to the contact (6) of the first internal electrode (2). The first contact (6) is connected to the potentiostat/galvanostat, while the contact (7) of the second internal electrode (3) is disconnected. Then, the open sides (2'') of the plates (2') of the first electrode (2) are electrochemically modified by coating with a metal or other modifying material layer. The same principles apply if two or more capacitors are used instead of one.

After the electrochemical deposition of the metal and/or other modifying substances, the solution is replaced by the electrochemical deposition solution of the metal and/or other modifying substances for deposition on the exposed sides (3'') of the second electrode (3). An electrical potential is applied to the contact (7) of the second electrode (3). The second contact (7) is connected to the potentiostat/galvanostat, and the contact (6) of the first electrode (2) is disconnected. Thus, the open sides (3'') of the plates (3') of the second electrode (3) are electrochemically modified by coating with a metal layer. The same principles apply if two or more capacitors are used instead of one.

The open sides (2'', 3'') of the plates (2', 3') of the electrodes (2, 3) are electrochemically coated with a metal layer consisting of inert and/or electrochemically active metals such as gold Au, platinum Pt, palladium Pa, ruthenium Ru, titanium Ti, copper Cu, manganese Mn, iron Fe, cobalt Co, aluminum Al, zinc Zn, or an electrodeposited alloy formed from these metals and/or another electrodepositable material, e.g. electrochemically formed conducting polymers such as polypyrrole, polyaniline, polythiophene, poly(3,4-ethylenedioxythiophene). The material of the deposition layer is selected taking into account the function of the electrodes (2, 3) in a specific electrochemical system. Open electrodes (2, 3) plates (2' , 3') sides (2'', 3'') are electrochemically modified to ensure greater stability and/or electrocatalytic activity.

In the case where the multilayer ceramic/metal capacitor (C) has more than two electrodes where each electrode would have an exposed side after removing the insulating coating from the side of such multilayer ceramic/metal capacitor exposing the sides of all the electrode plates, the manufacturing procedure of the electrochemical cell is the same , as described above. In this case, the exposed sides of each electrode plate would be coated in the manner described above.

As shown in Figure 11, after electrochemical deposition, the sides (2'') of the metal electrode plates (2') of the first internal electrode (2) and the sides (3'') of the metal plates (3) of the second internal electrode (3) located in the coating ( 4) in the open area (5) on the side of the multilayer ceramic/metal capacitor (C), immersed in the liquid electrolyte solution (10).

In the same way as described above, two or more capacitors can be processed simultaneously or sequentially - one after the other, to form an electrochemical cell consisting of two, as shown in Figure 12, or more capacitors, each having two electrodes.

A matrix of electrochemical cells can be formed, consisting of individual electrochemical cells, each of which consists of two or more multilayer capacitors, thus it is possible to form multi-channel electrochemical systems using a multi-well enzyme-linked immunosorbent assay (ELISA) )) plates or similar systems with many analysis channels as shown in Figures 13 and 18.

In all embodiments of the invention, the electrochemical cell includes at least one working electrode, at least one reference electrode, and at least one auxiliary electrode, wherein each electrode of such cell includes the exposed sides of the capacitor plates.

In all embodiments of the invention, the electrochemical cell includes at least one working electrode, at least one reference electrode, and at least one auxiliary electrode, wherein each electrode of such cell includes the exposed sides of the capacitor plates. Additionally, in all embodiments, each electrode includes one or more interconnected capacitor plates.

In embodiments of the invention and according to the drawings presented in Figures 11 and 16, when the electrochemical cell consists of one multilayer ceramic/metal capacitor (C) comprising two electrodes (2, 3), as shown in Figure 2: one electrode is the working electrode (2), and the other electrode is the reference and auxiliary electrode (3).

In embodiments of the invention, when the electrochemical cell consists of two multilayer ceramic/metal capacitors (C), each of which includes two electrodes (2.1, 3.1; 2.2, 3.2), as shown in Figure 14, one electrode of each capacitor (2.1, 2.2) is the working electrode, one of the other two electrodes (3.1) of any of the two capacitors is the reference electrode, and another electrode (3.2) is the auxiliary electrode.

In the embodiments of the invention and as shown in Figures 12, 17, 20, when the electrochemical cell has two multilayer ceramic/metal capacitors, each of which includes two electrodes (2.1, 3.1; 2.2, 3.2): one electrode of one capacitor is the working electrode (2.1) , the other electrode of the same capacitor is the reference electrode (3.1), and both electrodes of the second capacitor are auxiliary electrodes (2.2, 3.2) acting as one auxiliary electrode. Such an electrode configuration is referred to in all embodiments as a three-electrode configuration, as shown in Figure 15 .

In a three-electrode cell, the electrodes (2.1, 3.1; 2.2, 3.2) can be electrochemically coated: the working electrode (2.1) can be electrochemically coated with inert and/or electrochemically active metals, such as gold Au, platinum Pt, palladium Pa, ruthenium Ru, titanium Ti, copper Cu, manganese Mn, iron Fe, cobalt Co, aluminum Al, zinc Zn or alloys of these metals. Electrochemically deposited alloys based on these and/or other metals can also be adapted for identical use in the electrochemical coating of the reference electrode (3.1), e.g. silver Ag is partially electrochemically converted to AgCl salt, forming an Ag/AgCl structure, which enables the Ag/AgCl structure to be applied as a reference electrode and used in three-electrode mode. The auxiliary electrode (2.2, 3.2) can be used uncoated, especially if it is made of titanium, since titanium is relatively inert. If some repairs require better electrochemical properties, this auxiliary electrode (2.2, 3.2) can be coated with inert and/or electrochemically active metals, such as gold Au, platinum Pt, palladium Pa, ruthenium Ru, titanium Ti, copper Cu, manganese Mn, iron Fe, cobalt Co, aluminum Al, zinc Zn or electrochemically deposited alloys of these metals.

In order to increase the selectivity of electrochemical cells, more advanced electrochemical modification of electrodes (2.1, 3.1; 2.2, 3.2) can be applied using various functionalized coatings (21), such as electrically conductive polymers or composites based on electrically conductive polymers, sol-gels or variously functionalized sol-gels, protein-modified silanized layers, DNA, RNA, covered with self-assembled monolayers or self-assembled monolayer-modified proteins, DNA, RNA, crosslinked, adsorbed or otherwise immobilized protein layers.

The electrode plates of most multilayer ceramic/metal capacitors are made of titanium.

In the particular case where the electrochemical cell has three electrodes, the reference electrode is made of silver electrochemically coated with silver chloride Ag/AgCl or another metal coated with layers of Ag/AgCl. The auxiliary electrode consists of any electrodeposited inert metals such as Au, Pt, Ti, Ag, Cr, Ni, Sn, or an electrodeposited alloy and/or a layered structure consisting of these and/or other metals.

According to one embodiment of the invention and as shown in Figures 16 and 17 , the electrochemical cell is a flow-through electrochemical cell, additionally according to the embodiments shown in Figures 11 and 12 , respectively, it includes a fluid flow system with fluid inlet (13) and outlet (14) tubes connected to external fluid pumping/suction systems. Such an electrochemical cell may include one multilayer capacitor comprising two electrodes (2, 3), where one of these electrodes is a working electrode (2) and the other electrode is an auxiliary and reference electrode (3); two capacitors, each of which includes two electrodes, used in any operating configuration of these electrodes (2.1, 3.1; 2.2, 3.2) as working, comparative or auxiliary electrodes; or by using more than two capacitors, each having two electrodes, which are used in any configuration where these electrodes are used as working, reference and auxiliary electrodes.

Using the ELISA plate-based system, each electrochemical deposition step can also be performed in the wells (12) of the ELISA plate, where each well (12) is designed to modify one multilayer ceramic/metal capacitor (C) or to modify several multilayer ceramic/metal capacitors (C) . Each well (12) of an enzyme-linked immunosorbent assay (ELISA) plate can be filled with a different electrochemical deposition solution to modify a multilayer ceramic/metal capacitor (C) or multiple capacitors (C) immersed in these wells. The system based on the ELISA plate can be applied both for the electrochemical deposition of metal and/or other modifying substances on the sides of several capacitor electrode plates, forming an electrochemical cell, and for electrochemical measurements.

An example of how materials are used for electrochemical deposition on electrodes (2.1, 3.1; 2.2, 3.2) in a three-electrode electrochemical cell configuration consisting of two multilayer ceramic/metal capacitors (C) will be discussed below. The structure of the electrochemical cell is the same as shown in Figures 12 and 17, and the electrode arrangement is the same as shown in Figure 15.

The working electrode (2.1) is coated as follows: the open sides of the plates of the working electrode (2.1) are additionally electrochemically coated with a metal layer formed from inert and/or electrochemically active metals, such as gold Au, platinum Pt, palladium Pa, ruthenium Ru, titanium Ti , copper Cu, manganese Mn, iron Fe, cobalt Co, aluminum Al, zinc Zn or electrodeposited alloys composed of these metals and/or other electrodepositable materials such as electrodeposited electrically conductive polymers, e.g. : polypyrrole, polyaniline, polythiophene, poly(3,4-ethylenedioxythiophene).

The reference electrode (3.1) is coated with a silver chloride Ag/AgCl structure or another metal coated with Ag/AgCl layers. The exposed sides of the plates of the reference electrode (3.1) are electrochemically coated with silver (Ag), which, in the presence of Cl- ions in the solution, is electrochemically partially transformed into the Ag/AgCl structure, enabling the use of the formed Ag/AgCl structure as the reference electrode (3.1).

The auxiliary electrode (2.2, 3.2) consists of two electrodes (2.2, 3.2) which are used without coating because they are made of titanium, which is relatively inert. In addition, if different electrochemical properties are required, the auxiliary electrode (2.2, 3.2) can be coated with inert and/or electrochemically active metals such as gold Au, platinum Pt, palladium Pa, ruthenium Ru, titanium Ti, copper Cu, manganese Mn, iron Fe, cobalt Co, aluminum Al, zinc Zn or their alloys deposited electrochemically.

Wires (8') connect the working electrode, the reference electrode and the auxiliary electrode to the respective potentiostat/galvanostat connections.

Additional coatings (21), membranes, can be used in the working zone limited by the open area (5), in the insulating coating of multilayer ceramic/metal capacitors (4). Such additional membranes increase the selectivity of the designed electrochemical cell, such as polycarbonate membrane, polypyrrole layer, etc., which reduce the permeability of some ions, or catalysts, e.g. enzymes such as glucose oxidase that form the layer/membrane.

An example of electrochemical coating of the electrodes (2.1, 3.1; 2.2, 3.2) of a three-electrode electrochemical cell is discussed below, where the amperometric glucose biosensor consists of two multilayer ceramic/metal capacitors (C). The structure of the electrochemical cell is the same as shown in Figures 12 and 17, and the electrode arrangement is the same as shown in Figure 15.

The working electrode (2.1) is formed from interconnected plates of the electrode (2.1), electrochemically coated with platinum (Pt) and then a layer of polypyrrole with embedded glucose oxidase.

The comparative electrode (3.1) is formed from the interconnected plates of the electrode (3.1), electrochemically coated with silver and later modified with silver chloride (Ag/AgCl).

The auxiliary electrode (2.2, 3.2) is formed from interconnected plates of electrodes (2.2, 3.2) made of pure titanium (Ti).

Insulated wires (8') connect the working electrode, the reference electrode and the reference electrode to the respective potentiostat/galvanostat connections.

An additional coating consisting of a polymeric, e.g., polycarbonate, membrane to protect the surfaces of the working and reference electrodes is used to cover the working zone limited by the exposed capacitor areas (5) in the multilayer ceramic/metal capacitor coating (4).

An example of the use of an electrochemical cell of the invention to construct an amperometric glucose biosensor is shown in Figure 20 and discussed below. The biosensor comprises an electrochemical cell comprising two multilayer ceramic/metal capacitors (C) in a three-electrode configuration according to the invention. The working electrode (2.1) is an electrode consisting of interconnected plates electrochemically coated with platinum Pt and polypyrrole with embedded glucose oxidase. The reference electrode (3.1) is an electrode consisting of interconnected plates coated with silver, electrochemically coated with silver chloride Ag/AgCl. The auxiliary electrode (2.2, 3.2) is an electrode consisting of interconnected plates made of pure titanium Ti. An insulated wire (8.1) connects the working electrode (2.1) to the corresponding potentiostat/galvanostat connector. An insulated wire (8.2) connects the reference electrode (3.1) to the corresponding potentiostat/galvanostat connection. An insulated wire (8.3) connects the auxiliary electrode (2.2, 3.2) to the corresponding potentiostat/galvanostat connection. Additional polycarbonate membrane coating (21) used for surface protection of working (2.1), reference (3.1) and auxiliary (2.2, 3.2) electrodes against electrochemically active substances and/or contamination with proteins and/or other interfering substances.

Although this description of the invention enumerates numerous parameters and advantages along with structural details and features, the description is presented as an exemplary embodiment of the invention. Without deviating from the principles of the invention, the details may be varied, in particular their shape, size and arrangement, taking into account the widely understood meanings of the terms and definitions used in the definition.

Claims (9)

A method of manufacturing an electrochemical cell comprising providing a multilayer ceramic/metal capacitor, wherein the multilayer ceramic/metal capacitor comprises a layered structure of a ceramic dielectric material, a first internal electrode comprising bonded plates, and a second internal electrode comprising bonded plates, wherein said layered structure is coated dielectric coating, the formation of an open area in the dielectric coating on one side of the multilayer ceramic/metal capacitor to expose the side of the layered structure, the side of the ceramic dielectric material layers, the side of the first internal electrode and the side of the second internal electrode, forming the working area of the electrochemical cell, is different in that after when an open area (5) is formed on the side of the dielectric coating (4) of the multilayer ceramic/metal capacitor (C), exposing the layers of the ceramic dielectric material (1), the sides (2') of the metal plates (2') of the first internal electrode (2) ') and the sides (3'') of the metal plates (3') of the second internal electrode (3), signal transmission means (8', 8'') for transmitting signals from the working area through the electrodes (2, 3) are connected to the contacts (6, 7) of the electrodes (2, 3), then the exposed area (5) is coated with an easily removable layer of protective material (9) to protect the working area from being coated with a solvent-resistant, long-term insulating material, then the electrodes (2, 3) contacts (6, 7) are coated with a long-term insulating material (11) in order to protect contacts (6, 7) from the solutions used during the following modification steps when the sides of the first and second electrodes (2, 3) are modified ( 2", 3"), then the layer of temporary protective material (9) is removed from the open area (5), once again exposing the sides (2'', 3'') of the first and second electrodes (2, 3), for further for processing, after that, the multilayer capacitor (C) is completely immersed in a solution for the electrochemical deposition of metals and/or other modifying substances on the exposed sides (2'') of the first electrode (2), where the electrochemical deposition of metals and/or other modifying substances during the process, the electric potential is applied through the contact (6) of the first internal electrode (2), where the first contact (6) is connected to the potentiostat/galvanostat, and the contact (7) of the second internal electrode (3) is disconnected at the time, after that, the solution for the electrochemical deposition of metal and/or other modifying substances is replaced by a solution for the electrochemical deposition of metal and/or other intended modifying substances on the open sides (3'') of the second electrode (3), for which the electric potential is applied through the second electrode (3) contact (7), where the second contact (7) is connected to the potentiostat/galvanostat and the contact (6) of the first electrode (2) is disconnected at the time, then electrochemically coat the metal plates (2') of the first internal electrode (2) ) sides (2'') and the sides (3'') of the metal plates (3') of the second internal electrode located in the open area (5) of the coating (4) on the side of the multilayer ceramic/metal capacitor (C) are immersed in the liquid electrolyte medium (10). A method according to claim 1, wherein the steps performed in the first claim are applied to two or more multilayer ceramic/metal capacitors (C) forming an electrochemical cell comprising more than two electrodes (2.1, 3.1; 2.2, 3.2). A method according to claim 1, wherein one electrode (2) is a working electrode and the other electrode (3) is a reference and auxiliary electrode. A method according to claim 2, wherein two or more multilayer ceramic/metal capacitors (C) are provided, each comprising two electrodes (2.1, 3.1; 2.2, 3.2), wherein one electrode of each capacitor (C) is a working electrode (2.1, 2.2), another electrode (3.1), not the same as any of the previously listed electrodes (2.1, 2.2), of the remaining electrodes, is the reference electrode, and yet another electrode (3.2), not the same as any of of the previously listed electrodes (2.1, 2.2, 3.1) is an auxiliary electrode. Method according to claim 2, wherein two or more multilayer ceramic/metal capacitors (C) are provided, each comprising two electrodes (2.1, 3.1; 2.2, 3.2), wherein one electrode (2.1) of one capacitor (C) is a working electrode , the other electrode (3.1) of the same capacitor (C) is the comparison electrode, and both electrodes of the second capacitor (2.2, 3.2) are auxiliary electrodes. A method according to any of the preceding claims, wherein the sides of the electrode plates (2, 3; 2.1, 3.1; 2.2, 3.2) exposed for interaction with the electrochemical deposition solution are electrochemically coated with a metal layer selected from inert and/or electrochemically active metals such as such as gold Au, platinum Pt, palladium Pa, ruthenium Ru, titanium Ti, copper Cu, manganese Mn, iron Fe, cobalt Co, aluminum Al, zinc Zn or their electrochemically deposited alloys, and/or other electrochemically deposited materials such as electrochemically formed electrically conductive polymers such as polypyrrole, polyaniline, polythiophene, poly(3,4-ethylenedioxythiophene), and the material of the deposition layer is selected depending on the function of the electrodes (2, 3; 2.1, 3.1; 2.2, 3.2) in a specific electrochemical system . A method according to any of the preceding claims, wherein each step of electrochemical deposition is performed in the wells (12) of an immunoenzymatic assay system plate, wherein each well (12) is designed to modify one multilayer ceramic/metal capacitor and/or several multilayer ceramic/metal capacitors. An electrochemical cell obtained by the method according to any one of claims 1-7. An electrochemical cell according to claim 8, comprising an integrated fluid flow system with fluid inlet (13) and fluid outlet (14) tubes connecting the cell to an external fluid suction/pumping system.